Abstract
The carbon supercapacitance strongly relies upon the electrolyte's nature, but the clear-cut structure-performance nexus remains elusive. Herein, a series of bio-carbons with gradually varied pore structure and surface chemistry are derived using a new salt template protocol (with eco-benign KNO3 as the template, activator, and porogen, and cheap gelatin as the carbon precursor), and are used as model systems to probe the dependence of the electrochemical mechanism of such nanocarbons on two typical electrolytes (KOH and EMIBF4). By only adjusting the KNO3 dosage, two pivotal figures of merit of biochar-multiscale porosity and surface functionalization-were finely modulated to construct electric double layers. Electrochemical data clarify that the combined porosity and doping effects all contribute to enhanced supercapacitance, but with only one of the two factors playing the leading role in different electrolytes. Kinetic analysis corroborates the fact that ample heteroatom doping can effectively compensate capacitance by intensive surface redox insertion in KOH, while a suitable pore size dispersion plays a preponderant part in self-amplifying the ion partitioning, and thus dictating a good charge separation in EMIBF4. A quasi-quantitative model of performance-structure relevance in EMIBF4 is judiciously conjectured to hint at a superb ion-pore-size compatibility, in which bi- or mono-layer ion confinement coupling in integrated single and double ion-sized pores is found to be more useful for curbing notorious over-screening effects and for changing the coordination number, Coulombic ordering, and phase conformation of EMIBF4 in several nm-sized nanopores. This unique energy storage fashion in ion-matching pores promotes the energy density of optimal samples to a novel level of 88.3 Wh kg-1 at 1 kW kg-1, which rivals the overwhelming majority of the reported carbon materials. In short, the comparison case study here reveals a valuable correlation of carbon's figure of merit and electrolyte type, which may act as a vital rudder to design electrolyte-contingent state-of-the-art supercapacitor materials.